MX2010013690A - Washable ink compositions and writing instruments comprising same. - Google Patents

Abstract

The disclosure is generally related to a washable ink composition and a writing instrument containing the same. The disclosure provides a washable ink composition that includes a pigment capsule having a polymer matrix formed of a resin selected from the group consisting of aminoplast resins, epoxy resins, and combinations thereof, and at least one colorant contained in the polymer matrix; and at least one washing aid having at least 4 ethylene oxide units per molecule of washing aid and/or at least one washing aid having an HLB value of at least 12.

Description

INK COMPOSITIONS WASHABLE AND INSTRUMENT WRITING THAT CONTAINS THEM Field of Invention The description generally refers to voidable composition and writing instruments that contain them in the description refers to composition vables that include a pigment capsule that has a contained colorant.

Background of the Invention The ability to wash clothes and other articles is a highly desirable quality for ink. Unfortunately, many trademark markers include ink compositions that are not a variety of fabrics and can thus leave stains on clothing and other articles made of fabrics.

Particularly, the washing ability or example, the observed color of the marks appears in pastel colors). In addition, many ink compositions take a significant amount to dry on white boards. Thus, ink compositions for dry erase marker pens can be washable for certain selected fabrics, the quality of the function and such markers is poor, and the markers are typically more for use by children.

Other ink compositions for marking disposable dry erase white canvases are capable of being erased from certain selected films such as chalk boards and / or other white polymer boards, easily removed from writing surfaces. higher quality targets (such as white boards having surface areas) a polymer matrix formed of a resin is the group consisting of aminoplast resins, the oxides, and combinations thereof, and at least one member in the polymer matrix; and, at least one ford having at least four oxide units r the washing aid molecule.

In a second embodiment, the description provides washable ink having a pig capsule is a polymer matrix formed of a resin of the group consisting of aminoplast resins, oxides, and combinations thereof, and at least one containing in the polymer matrix; and, at least one ford having a hydrophilic-lipophilic balance value of at least 12.

In another embodiment, the rinse-off ink composition or second embodiments further includes an aeration in sufficient quantity to provide a composition for the disposable washable ink composition according to the first and second embodiments of the ink deposition and additionally contains an emulsion agent. liberac In another embodiment, the description provides a marking of a written mark that consists in making a dry erase stratum with an ink composition in. dry according to the first or second modalid scription, the ink composition also contains an eration, and erase the mark.

Detailed description of the invention The ink compositions of the description have advantages, such as, for example, being substantially washable from clothes. Accordingly, the described ink can be substantially removed from a variety of fabrics, i.e., the marks pulled from a variety of fabrics without leaving a stain. In addition, when the tint combinations are attributable to the characteristics that result from the surface surfaces of the materials selected for olimmeric (for example, the surface characteristics of the outer surfaces of the pigment capsules), a wash aid has at least one For example, it is believed that the capsules of the pigment escription have no significant affinity for four ethylene oxide (preferable repeat units) per molecule of the washing aid and / or hydrophilic-pyrophilic balance ("HLB"). Many functional groups to link to the potential binding sites in the selected washing units are associated with the outer ones of the pigment capsules via their drofobics to prevent any interaction of the rectum between the pigment capsules and the pigment capsules. any point) in the fabrics, the spotting interactions with ink blends described.

One aspect of the disclosure is a volatile composition that includes a polymeric precursor pigment capsule formed of a resin selected from the aminoplast resin, epoxy resins, and at least one dye contained, dissolved, and / or dispersed within. of the polymer matrix or at least one washing aid which has at least ethylene oxide per molecule of the assistant of n HLB value of at least 12.

Another aspect of the description is an instrument that contains a washable ink composition according to the invention.

In another aspect, the tint-washable compositions further include a release agent for printable washes of dry-cleaning ink.

Another aspect of the invention relates to a dry cleaning instrument described herein, and to erase the mark. pigment capsule The pigment capsule has a poly-matrix containing at least one dye. Typically, the color nte, but pigments could also be used.

The pigment capsules are formed by dispersing, dissolving, or distributing a dye in the polymer matrix from other manners.

The pigment capsules can be formed by the technique, for example, by emulsifying a resin on an epoxy resin, adding a hardening agent, and then polymerizing the resulting mixture, US Pat. Nos. 2,498,592, 869,184, whose descriptions they are incorporated into an The dyes can be added in any invention, such as, for example, during the formation d after the formation of the resin, or after the use of the alkyl; (2) carboxylic acids, carboxylates, or their derivatives esters) including, but not limited to, acrylics and acrylates such as butyl acrylate, acrylhexyl, ethyl acrylate, and methacrylates, and (3) n clue but are not limited to acrylonitriles, xcfuir from the reaction mixture.

Examples of suitable aminoplast resins are not limited to, formaldehyde of urea, formal lelamine, formaldehyde of benzoguanamine, and their substituted with alkyl and aryl, for example formally ethylurea, formaldehyde of phenylurea, formaldehyde of amino-1, 3,5- triazine, formaldehyde of 2,4,6-trimethyltriamiazine, and the like. Other convenient examples are condensation products of urea, melamine, annaline, uanidine, dicyandiamidine, and benzoguanamine with ald, eg, acrolein, butyraldehyde, formaldehyde, paraformal, butylhemiformal, bis adduct. Preferred resins include resins of the for resins of formaldehyde of urea and rmaldehyde of melamine, resins of benzoguanamine, polides.

Other suitable matrices of the polystyrene polymer, polystyrene modified with polycarbonate, p-or v i n-I chloride, and polyamide. See American Nos. 5,714,090 and 5,740,502.

Generally, any dye can be used as a colorant in the polymeric matrix since the capacity of the ink compositions is believed to be derived from the surface characteristics attributable to the selected polymer and the aided auxiliaries, as described herein. Convenient dyes such as dye include, but are not limited to, basic, acid dyes, solvent dyes, straight fluorescent dyes, or other dyes compatible with the polymer matrix. , 11, 12, 27, 28, 33, 34, 39, 50, 58, 86, 100, 106, 107, 32, 142, 157, and the like); onazoic anthraquin dyes; diazo dyes; phtha derivatives including, for example, various sulfonatal talcocyanine salts; azoanulenes; formazan ridenodioxazine complexes; bernacida red 2BMN; Pontaine dyes, bright blue A, Pontamine®; Bright red Cib ie red reactive 4) (Aldrich chemical); Red brillant lecir, red reagent 56) from Drimarene (Piloam, Inc.); Red B (Mobay Chemicals, Haledon, New Jersey) by Lev • Tillante E-6BA Levafix® (Mobay Chemical); Procíon® H eir, reactive red 31) (ICI America); Crude ground shines Dsa B direct, (Crompton &Knowles); artasol pressed mass GTF (Sandoz, Inc.); liquid yellow specific artasol GTF (Sandoz, Inc.); yellow shade 1694 asacid X34 black (ie BASF X-34) (BASF); Sandoz black, Inc.); Neozapon Red 492 (BASF); Orasol G Ciba-Geigy); black Savinilo RLS (Sandoz); Dermaca Sandoz); black Pyrazol BG (11); Concentrate A of lorfast (Morton-Thiokol); black Diazol RN Quad (11); a (Ciba-Geigy); blue Savinilo GLS (Sandoz, Inc.); blue L Morton-Thiokol); Sevron blue 5GMF (101); Basacid Blue 7 eye Bernacid (Berncolors, Poughkeepsie, N.Y.); Berncol marillo fast 4GL-175 of curtain, black Basacid SE 022 several reactive dyes, including reactive black dyes, eactive, reactive red dye for example red reactive imilar, yellow reactive dyes including e tactivo 37 and the like; and its mixtures.

Polymeric dyes are also convenient for coloring dyes in the washable ink composition. Representatives include, but are not limited to, dyes produced by Milliken Corporation (Spartanburg, SC) in Palmer dye products. n l These include but are not limited to alkocyanin pigm, quinacridone pigments, nimidezolomide pigment, beta-naphthol pigments, rbon pigments. Specific pigments include but are not titanium dioxide, zinc oxide, calcium carbonate, loin (lead carbonate), barium sulfate, iron blue, ultramarine blue, iron oxide black (oxide of!), Stick of Campeche, brown iron oxide, red iron red, cadmium yellow (CDs, CdZnS), a turmeric, yellow iron oxide, chromakey oxide, ferrocyanides, ferricyanides, manganese ammonium irophosphate violet), several salts of successively. The pigment precursors c in US Pat. No. 6,524,382. so they are this application.

The pigment capsule can be included in one ink in a range of about 1% in that washing ui iar In one embodiment, the compositions described include at least one washing aid having at least 8 ethylene oxide units, at least 20 units of ethylene oxide, and 30 units of ethylene oxide. , per molecule of the ford. Such washing auxiliaries typically have at least 6, an HLB value of at least 8, a value of at least 10, and / or an HLB value of at least 12, or auxiliary washing agents can have an H value. Approximately 6 and approximately 19. Thus, they are co-auxiliaries of washing of the high polarity with values dr at least 6, such as alkyl sulfonates and amine oxides. When at least one washing aid, the use of the ink does not include at least 4 ethylene units per molecule of the washing aid, because of the washing content of the composition of the ethoxylated fatty alcohol, ethoxylated fatty acid, and Xyliary washing polyol indispensable can be included in the ink in a range of about 0.5% and about 20% by weight, about 1% about 20% by weight, 2% by weight to about weight, and / or about 4% by weight. % by weight to 10% after auxiliaries or washing surfactants, in addition to laundry washing which has at least four ethylene units per washing aid molecule and / or with at least 12 LB can also be included, plicated in additional detail below. liberation people If a dry wiping formulation is desired, a blink can be included. After use, an emulsion typically migrates from the composition of the surface of the white board and thereby forms a surface of the white board (composition of the hemicals Inc.), hexyloenoglycol (Ashland Inc.). The addition can be included in the composition of the ink at about 2% by weight to 20% by about 5% by weight to about 15% by weight.

Washable ink compositions also include a. solvent. Suitable solvents include, itán a, alcohols, deionized water, aro tones compounds. For example, the solvent may include methanol, butanol, phenols, butanone, acetone, 2-orpholine, N-methylpyrrolidinone, dimethyl methylformamide, dimethyl sulfoxide, clohexylpyrrolidone, thiodiethanol, thiodiglycerol, sulfolane, propylene, ethylene carbonate, glycerol, f methylformamide, and N-methylpyrrolidinone. Toxics are preferred, such as ethanol and deionized water. The conveniences include, but are not limited to, polyvinyl (erivatives, polyvinyl alcohol, polyvinyl-olyacrylic acids and their derivatives, d-alaic anhydride polymers, and methyl cellulose and its derivatives.) The binder is included in the ink composition in a range of about I by weight to 30% by weight, about 2% about 20% by weight, and / or about 3 about 10% by weight. nstruments of writing Convenient writing instruments for its omission of washable ink include, but are not limited to, such as, for example, stacking markers, valve action markers, and similar capillary action markers generally include or store the ink composition. washable, fluid communication with a porous tip. The marker to be included includes an i i r and about twenty-five centipoise (cps), about one and about twenty, about one and about fifteen cps, inco cps and about fifteen cps. However, provided above may increase or decrease, depending on the nature and porosity of the tips and / or the den of the ink deposits (if they are employed).

Additives The ink may optionally contain other additives, for example, biocides, stress modifiers after synergistic resins, surfactants or auxiliary surfactants, dispersing agents and / or other additives as a technique. Washing auxiliaries or film surfactants for use in the compositions described include, but are not limited to, the glycol derivatives Hes such as Surfynol 440 and Surfynol 502. These additives refer to the ink compositions in an amount EXAMPLES The ink compositions of each of them were loaded in a marker and tested for erasing (MEF). The ink compositions also stolen as to the washing ability of example 1 A blue ink was prepared by mixing the esionized eta, attaching it to polyvinyl KW-3, Triton X-305, and ÍL6182 in a reaction flask with a mixer for about 15 to 30 minutes. The IL-WET® L-7607 agent and Surfynol 440 surfactant are added to the reaction flask, and the mixing continues for an additional 10 minutes. The auxiliary riton® X-305, is an octylphenol ethoxylate with ethylene group by the washing aid molecule, and a val 17.3. The ingredients were used in the j r Surfynol® 440 Surfactant 2 Triton® X-304 Wash aid 6 (octyphenol ethoxylate) The ink was loaded in a marker for the ability to erase and wash.

Example 2 A blue ink was prepared following the procedure (example 1), except that Triton® X-705 was used instead of 5. The washing aid, Triton® X-705, is an ethyphenylphenol with 55 ethylene oxide groups per m. washout, and a HLB value of 18.5.The ink was n marker for the erasability test and sample 3 Blue ink was prepared following procedure 1, except that Ethofat® 242/25 was used instead - ethylene oxide per washing aid molecule, and an e 9.8. The ink was loaded in a marker for the erase and wash facility. comparative example 2 Blue ink was prepared following procedure 1, except that Armeen® 18D was used instead of 5. The washing aid, Armeen® 18D (Akzo Nobel, Ch s an aliphatic amine having 0 oxide groups of the auxiliary washing, and an HLB value of 8. L on a marker for the e washing capacity test.

Comparative Example 3 Blue ink was prepared following procedure 1, except that Laropal® A81 (BASF, Fleet Park used instead of Triton® X-305) Washer 81, is an aldehyde dispersion resin having 0 x Ethylene or the ILWET® L-7607 wash aid molecule and Surfynol® 440 surfactant were added to the reaction flask and continued for about 10 minutes.The lava aid -100 is an octylphenol ethoxylate with 9.5 thylene groups per molecule of the washing aid and a value 3. 5. The washing aid, Ethofat® 242/25, is an ami toxylated with 15 moles of ethylene oxide, and an HL value of the dye, MP series, includes a polymer matrix of formaldehyde resin. The ingredients were used in the amounts shown below.

Component Function Ca \ zul MP-BL6182 Pigment Caplet 10 (formaldehyde resin) Ethanol Solvent 62 W-3 (20%) Binder 13 Deionized solvent Solvent 2% erase and wash ability.

Example 5 The procedure of Example 4 was followed, except that anax FB 403 was used instead of the blue MP-BL pigment capsules to produce a red ink. The nucleus, Panax FB, includes a polymeric form of benzoguanamine formaldehyde matrix. The ink was charged to the erasability test and the comparative sample 4 The procedure of Example 4 was followed, except that 3 of Irgalite® CG2 (Ciba, Basilea, Switzerland) was used zul MP-BL6182 as the orange printable pigment capsules. The pigment capsules, Irgalite® CG na polymer matrix formed of a rhelide / melamine-formaldehyde. The ink was load arcador for the proof of capacity of erasure and lav Component Function Ca Blue Lumikol NKW3204C Pigment Caplet 25 Ethanol Solvent 49 KW-3 (20%) Binder 13 Silwet® L-7607 Release agent 5% Surfynol® 440 Surfactant 2% Triton® X-304 Wash aid 2% (octylphenol ethoxylate) Ethofat® 242/25 Wash aid 4% (ethoxylated aliphatic amine) The ink was loaded in a marker for the erase and wash facility. comparative example 6 The ink was loaded in a marker for the erase and wash facility. results of the washing capacity test The washing ability of the stolen compositions using pieces of multi-fiber fabric (Testfabrics, ttston, PA) that contains the desired type of fabric and lava typical residential washing machine. The markers for test inks were used to mark approximately 2.54 cm (1 inch) in each piece. The labeled fabrics were dried at least 15 hours before lightening, the marked fabrics were fixed to simile safety sheets. A washing machine was charged with the 1 powder detergent, the simulated sheets (approximate) and the test samples to make approximately 2 kg. The water level was set to idle, the temperature conditions of the cycle c 1 2 3 4 No stain spot stain severe moderate light spots visible only remain Great loss p washed out small loss in moderate traces of that of the intensity intensity colored color but remain the brands The results of the capacity tests of They are shown in table 1 below.

ABLA 1: RESULTS OF THE PROOF OF THE CAPACID AVADO Fabric wash capacity (5 point scale) Polyester Acrylic Cotton Polyester bleached 61 54 64 Example 1 1 1 1 1 Example 2 1 1 1 1 Example 5 1 1 1 1 Example 3 4 4 4 comparative 4 Example 2 2 1 2 comparative 5 Example 4 4 1 1; Comparative 6 As these results show, the compositions according to the description can be completely removed from a variety of fabrics without leaving a sible. The results also show the importance of washing and the polymeric matrix for pro Printing of ink that can be washed successfully from a 3 fabrics.

Only movement. For a given white board, two lines drawn across the length of the board surface on a marker that has the ink loaded. The ability to erase the test lines in a single time was determined using the minimum equipment of the test. The MEF equipment was attached to a braze holder and anchored to a speed traction shaft and aluminum alloy has dimensions of 5 cm x 4 x x x 50 g and with a eraser pad fixed on one side. The luminance was placed at least 2.5 cm above the lines with weight of 100g. The aluminum block inserted perpendicularly through the variable speed pru otor lines at a speed of approximation n / s ± 0.1 to effect the erasure of the complete pru-rred lines was not reached in one movement, the c oque of aluminum was increased in increments of ??? _? 2: TEST RESULTS OF THE 0RRADO FORCE The compositions of the ink according to the ferally required a less force or equivalent

Claims (1)

1. CLAIMS 1. A washable ink composition having: (a) at least one capsule of the polymeric pigment which is formed of a selected resin consisting of aminoplast resins, epoxy resins or ombinations; and at least one dye contains polymeric attrition; Y, (b) at least one wash aid that preserves logs 4 units of ethylene oxide per wash molecule. 2. The washable ink composition claimed by the resin is an aminoplast resin that is a by-product of the reaction of an aminoplast crosslinker. 3. The washable ink composition claimed in the aminoplast crosslinker is selected from the insistent urea, melamine, annaline, ammeline, 5. The washable ink composition of at least one washing aid is selected from ethoxylated alkylphenol, alkoxylated alcohol, ethoxylated fatty acid, and ethoxylated lipase polyethylene glycols. 6. The washable ink composition of the present invention is at least 0.5 wt.% At about that of the ink composition. 7. The washable ink composition of at least one washing aid has a hydrophilic-lipophilic (HLB) balance of at least 6. 8. The washable ink composition of at least one wash aid has a hydrophilic-lipophilic balance (HLB) of at least 12. 9. The washable ink composition of the claimed: > In the at least one pigment capsule pr 12. The washable ink of claim 11, in light is polar. 13. The washable ink composition of the claim wherein the solvent is selected from the group of deionized covalent, methanol, ethanol, propanol, butanol, utanone, acetone, 2-pyrrolidine morphoin ethyl pyrrolidinone, dimethyloacetamide, dimethyl dimethyl sulfoxide, formamide, cyclohexyl opiothiethanol , thiodiglycerol, sulfolane, carbonate of ethylene rbonate, glycerol, formamide, dimethylfor-methylpyrrolidinone. and its combinations. 14. The washable ink composition of the present invention also has a release agent. 15. The washable ink composition of the claim wherein the release agent contains from about 1 weight to about 20% by weight of the composition. and carboxylic acids. 19. A writing instrument having the washable ink coater of claim 1. 20. A washable ink composition that presents: (a) at least one polymeric pigment capsule formed from a resin selected from aminoplast resins; epoxy resins; and at least one polymeric containing dye; Y, (b) at least one wash aid having a hydrophobic-lipophilic balance (HLB) of at least 12. 21. The washable ink composition of the claim wherein the resin is an aminoplast resin that is a by-product of the reaction of an aminoplast deic acid crosslinker. 22. The washable ink composition of the claim where the aminoplast crosslinker is selected rfural, phthalatedehyde, and tereftaldehyde. 24. The washable ink composition of the claim wherein the product of the reaction is substantially repeating units having carboxylic acid sulfonamides, carboxylates, and arboxylate derivatives. 25. The washable ink composition of the claim wherein at least one wash aid is selected consisting of octylphenol ethoxylate and toxylated amines. 2. 6. The washable ink composition of the claim further presents a release agent. 27. Dry erase board having a sea contains the ink of claim 26. 28. The washable ink composition of the claim also contains at least one binder soluble in 29. A writing instrument that pre